CN104193955A - Fluorine-containing aromatic polyester-siloxane segmented copolymer as well as preparation method and application thereof - Google Patents
Fluorine-containing aromatic polyester-siloxane segmented copolymer as well as preparation method and application thereof Download PDFInfo
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- CN104193955A CN104193955A CN201410454529.0A CN201410454529A CN104193955A CN 104193955 A CN104193955 A CN 104193955A CN 201410454529 A CN201410454529 A CN 201410454529A CN 104193955 A CN104193955 A CN 104193955A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4607—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen having halogens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
Abstract
The invention relates to a fluorine-containing aromatic polyester-siloxane segmented copolymer as well as a preparation method and application thereof, and belongs to the technical field of preparation of a high-molecular polymer. The fluorine-containing aromatic polyester-siloxane segmented copolymer is prepared by mixing terminated hydroxyl polysiloxane, diisocyanate, a catalyst and a solvent, and reacting for 2-5h at 60-100 DEG C; adding terminated hydroxyl fluorine-containing aromatic polyester, and reacting for 1-5h at 60-100 DEG C. The segmented copolymer disclosed by the invention is relatively low in surface energy, and excellent in hydrophobic performance and oleophylic performance; the segmented copolymer can be used for preparing an oil-water separation membrane and is applicable to oil-water separation; according to the prepared oil-water separation membrane, a water contact angle is more than 120 degrees and a contact angle of the membrane and oil is reduced to be less than 5 degrees within 1s in air.
Description
Technical field
The present invention relates to a kind of fluorine-containing aromatic polyester-silicone block copolymer and its preparation method and application, belong to high molecular polymer preparing technical field.
Background technology
Along with the quickening of urban industry process, the mankind's environmental consciousness improves gradually.Oily(waste)water is the important environmental pollutant of a class, and in the sewage of the discharge of petroleum and chemical industry industry, contains a large amount of oil, and the overwhelming majority is nonpolar oils, compared with difficult for biological degradation.Oil easily generates air-locked oil film in water, and impact, when the ecotope of body, is also one of major reason of water pollution.Oily water separation technique field is mainly to use water-and-oil separator at present, but equipment complexity, energy consumption is higher, cost is higher is a difficult problem for restriction industry development.Oily water separation membrane technique also stays in the experimental phase at present, and industry changes into product condition deficiency.Therefore can find one economical and practical, can remove continuously again the oily water separation membrane preparation method of the water in oil, be the important topic of whole filtration industry.
The preparation method of at present existing many patent report oily water separation films, as application number is 201310309217.6,2012101445713,200810100985.X, 201210435983.2,201310027762.6, the patents such as 201310224027, although have good oil-water separation, have the problems such as water-fast solvability, the swelling property of separatory membrane be poor.The research of fluorine-containing poly aromatic polyester-silicone block copolymer oily water separation film prepared by the present invention there is not yet relevant report in the literature.
Summary of the invention
The object of the present invention is to provide a kind of segmented copolymer, the preparation method of this segmented copolymer and purposes and the product that adopts this segmented copolymer to be prepared into.
Technical scheme:
A kind of segmented copolymer provided by the present invention is: fluorine-containing poly aromatic polyester-silicone block copolymer, and its structural formula is as shown in Equation 1;
Formula 1
In formula 1, the random natural number that n is 10-250, the random natural number that m is 50-600;
。
Above-mentioned fluorine-containing aromatic polyester-silicone block copolymer, its number-average molecular weight is 20000-180000; Its surface has lower surface energy, has excellent hydrophobic performance and oleophylic performance.
The present invention by further experiment study the value of discovery: n and m, substituent selection respectively the performance such as the weather resistance on this segmented copolymer oily water separation film, dissolubility resistent, circulation there is important impact.The introducing of fluoro-containing group has the surface energy that utilizes reduction separatory membrane, improves its hydrophobicity.Get other values with respect to n, m, in the time of n=100-150, m=300-400, the oily water separation performance of this segmented copolymer is better, and separating effect is obvious.
The present invention also provides: wherein a kind of preparation method of fluorine-containing aromatic polyester-silicone block copolymer of the present invention, after the steps include: hydroxy-terminated polysiloxane, vulcabond, catalysts and solvents to mix, in 60-100 DEG C of reaction 2-5 hour; Then add terminal hydroxy group fluorine-containing aromatic polyester, in 60-100 DEG C of reaction 1-5 hour; And then except desolventizing;
Used catalyst is: dibutyl tin laurate and/or dibutyltin diacetate;
Solvent for use is: one or more in tetrahydrofuran (THF), phenylfluoroform, trichloromethane and methylene dichloride.
Above-mentioned preparation method, the consumption of used catalyst is preferably the 0.1-2% of hydroxy-terminated polysiloxane, vulcabond and the fluorine-containing fragrant total mass of terminal hydroxy group.
Above-mentioned preparation method, the mol ratio of terminal hydroxy group fluorine-containing aromatic polyester, hydroxy-terminated polysiloxane and vulcabond can be determined according to the structure of product, be preferably 1:0.5-2:2.1-3.
Above-mentioned preparation method, the structural formula of terminal hydroxy group fluorine-containing aromatic polyester used is:
；
In formula,
, the random natural number that n is 10-250;
To be prepared from by copolycondensation by fluorine-containing bis-phenol based compound, m-phthaloyl chloride and p-phthaloyl chloride.
The method of preparing terminal hydroxy group fluorine-containing aromatic polyester taking fluorine-containing bis-phenol based compound, m-phthaloyl chloride and p-phthaloyl chloride as raw material is that those skilled in the art can obtain from prior art; In the specific embodiment of the present invention, also provide concrete operation step.Fluorine-containing bis-phenol based compound used, refers to that in bis-phenol based compound, more than one hydrogen atom is replaced by fluorine; Bis-phenol based compound means the compounds that two hydroxyphenyl are coupled together by one or more carbon atoms.Fluorine-containing bis-phenol based compound of the present invention is bisphenol AF, 1, two (4-the hydroxyphenyl)-1-phenyl trifluoromethanesulfonate ethane of 1-and trifluoromethyl Resorcinol.
Above-mentioned preparation method, hydroxy-terminated polysiloxane used is the poly-methyl trifluoro propyl siloxanes of hydroxyl-terminated injecting two methyl siloxane or hydroxyl; Its number-average molecular weight is 3000-40000.
Above-mentioned preparation method, vulcabond used is the one in tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI) and hexamethyl vulcabond (HDI).
Above-mentioned preparation method, its specific operation process is as follows:
(1) vulcabond is dissolved in to partial solvent, then adds hydroxy-terminated polysiloxane, catalyzer, stir and form inorganic phase, in 60-100 DEG C of reaction 2-5 hour;
(2) step (1) continues to add remaining solvent and terminal hydroxy group fluorine-containing aromatic polyester after completing, in 60-100 DEG C of reaction 1-5 hour, then except desolventizing obtains fluorine-containing aromatic polyester-silicone block copolymer.
Study discovery by further experiment, the reaction of step (1) is carried out under nitrogen protection condition, can improve the productive rate of product.
In view of, the surface of fluorine-containing aromatic polyester-silicone block copolymer of the present invention has lower surface energy, has excellent hydrophobic performance and oleophylic performance; So the present invention also provides the application of this segmented copolymer for oily water separation.
The present invention also provides: a kind of fluorine-containing poly aromatic polyester-silicone block copolymer of the present invention is for the application of oily water separation.Concrete, fluorine-containing aromatic polyester-silicone block copolymer of the present invention is as the application of oily water separation film.
The present invention also provides: a kind of oily water separation film of being made up of fluorine-containing aromatic polyester-silicone block copolymer, be fluorine-containing aromatic polyester-silicone block copolymer of the present invention to be dissolved in in solvent, to be made into massfraction be 1-25% solution, then this solution be coated in to dry forming in fabric web.
Above-mentioned oily water separation film, water contact angle is greater than 120 °, in air to being reduced to below 5 ° in the oily contact angle short period of time (in 1s),
Solvent for use is: one or more in tetrahydrofuran (THF), phenylfluoroform, trichloromethane and methylene dichloride.
Described dry referring to: in 30-100 DEG C of dry 8-72 hour.
Described fabric web is the one in 100-500 object copper mesh, iron net, glass fiber mesh and plastic wire.Be preferably copper mesh, the relatively nonmetallic glass fiber mesh of copper mesh and plastic wire have good solvent resistance.Strong with respect to iron net erosion resistance.
Beneficial effect
Fluorine-containing aromatic polyester-silicone block copolymer of the present invention surface has lower surface energy, has excellent hydrophobic performance and oleophylic performance, can be used in separation profit.The oily water separation film that adopts this multipolymer to be prepared from, water contact angle is greater than 120 °, in air to being reduced to below 5 ° in oily contact angle 1s.Adopt this multipolymer to be easily prepared into oily water separation film, can large-area applications, be beneficial to industrialization.Oily water separation film of the present invention is strong to oily penetrating power, and oil is had to lower adhesivity, not only separating but also can be used for separating of segment polarity oil and water for non-polar oil and water mixture.The preparation method of front end multipolymer of the present invention, synthetic easy with preparation method, the gentle easily control of reaction conditions, is easy to suitability for industrialized production.
Embodiment
embodiment 1
the preparation of terminal hydroxy group aromatic polyester: first in four-hole bottle, add 10.5g 1, two (4-the hydroxyphenyl)-1-phenyl trifluoromethanesulfonate ethane of 1-, 2.65 g NaOH, 80 ml deionized waters and 0.051 g phase-transfer catalyst Tetrabutyl amonium bromide, stirring is dissolved in two (4-the hydroxyphenyl)-1-phenyl trifluoromethanesulfonate ethane of 1,1-and in water, is made into inorganic phase.P-phthaloyl chloride and the each 2.90g of m-phthaloyl chloride are dissolved in to methylene dichloride 150 ml and are made into certain density organic phase.Be at 10 DEG C, organic phase to be splashed in inorganic phase in temperature, after stirring reaction 1 hour, improve temperature, below 20 DEG C, stirring reaction adds dilute hydrochloric acid washing to neutral after 3 hours, after dry, obtain terminal hydroxy group aromatic polyester, adopt GPC-MwA type gel chromatograph, recording aromatic polyester number-average molecular weight is 26300.
the preparation of fluorine-containing aromatic polyester-silicone block copolymer: will0.12g '-diphenylmethane diisocyanate (being called for short MDI) is dissolved in the tetrahydrofuran (THF) of 1.01g.In four-hole bottle, add the '-diphenylmethane diisocyanate, 0.95g hydroxyl-terminated injecting two methyl siloxane (number-average molecular weight is 10000), 94.15g tetrahydrofuran (THF), the 0.025g dibutyl tin dilaurate that have dissolved; stirring is dissolved in hydroxyl-terminated injecting two methyl siloxane and in tetrahydrofuran (THF), is made into inorganic phase; rising temperature to 65 DEG C is also reacted 3 hours at this temperature, in reaction process using nitrogen as protection gas.Then, add the 5.03g terminal hydroxy group aromatic polyester of above-mentioned preparation in four-hole bottle, temperature remains unchanged again, react 5 hours, be cooled to room temperature, adopt to revolve and steam instrument by the solvents tetrahydrofurane of going out in product, after being dried, obtain fluorine-containing aromatic polyester-silicone block copolymer.Adopt GPC-MwA type gel chromatograph, the number-average molecular weight that records this fluorine-containing aromatic polyester-silicone block copolymer is 77000.
the preparation of oily water separation film and oily water separation experiment:be dissolved in tetrahydrofuran (THF) to be made into massfraction be 10% solution getting above-mentioned product, under magnetic agitation, make fluorine-containing aromatic polyester-silicone block copolymer be dissolved in tetrahydrofuran (THF) and make polymers soln.Fluorine-containing aromatic polyester-silicone block copolymer solution is evenly sprayed on 300 object copper mesh with spray gun to dry aromatic polyester fluorine-containing aromatic polyester-silicone block copolymer oily water separation film that obtains for 16 hours.(area is 12cm to the oily water separation film of preparation
2) be fixed in homemade oily-water seperating equipment, by dye red water and colourless ethyl acetate (representing polar oil) 1:1 mixing and stirring by volume with red prepared Chinese ink, in 10 seconds, 50ml oil-water mixture is poured in oily-water seperating equipment.Can find that ethyl acetate is also penetrated into and is connect in liquid bottle by separatory membrane rapidly in 10s, and red water is blocked on separatory membrane.
embodiment 2
the preparation of terminal hydroxy group aromatic polyester: first in there-necked flask, add 10.14 g bisphenol AFs, 2.64 g NaOH, 100 ml deionized waters and 0.045 g phase-transfer catalyst Tetrabutyl amonium bromide, stir and bisphenol AF is dissolved in water, be made into inorganic phase.4.05g p-phthaloyl chloride and 2.03g letter phthalyl chloride is dissolved in to 150 ml methylene dichloride and is made into certain density organic phase.Be at 5 DEG C, organic phase slowly to be splashed in inorganic phase in temperature, stirring reaction, after 2 hours, improves temperature, stirring reaction 3.5 hours below 10 DEG C.Product is washed till to neutrality with dilute hydrochloric acid, obtains terminal hydroxy group aromatic polyester after dry, adopt GPC-MwA type gel chromatograph, recording terminal hydroxy group fluorine-containing aromatic polyester aromatic polyester number-average molecular weight is 48000.
the preparation of fluorine-containing aromatic polyester-silicone block copolymer:tolylene diisocyanate 0.11 g is dissolved in the tetrahydrofuran (THF) of 2g, then in four-hole bottle, add the tolylene diisocyanate having dissolved, the poly-methyl trifluoro propyl siloxanes (number-average molecular weight 8000) of how many 0.87g terminal hydroxy group, 95.15g tetrahydrofuran (THF), 0.02g dibutyltin diacetate, stirring is dissolved in the poly-methyl trifluoro propyl siloxanes of terminal hydroxy group in tetrahydrofuran (THF), to be made into inorganic phase and to pass into nitrogen, and rising temperature to 65 DEG C is also reacted 10 hours at this temperature.Then in four-hole bottle, add again the terminal hydroxy group aromatic polyester 5.23g of above-mentioned preparation, temperature remains unchanged, and reacts 5 hours, is cooled to room temperature, employing is revolved and is steamed instrument by the solvents tetrahydrofurane of going out in product, after being dried, obtains fluorine-containing aromatic polyester-silicone block copolymer.Adopt GPC-MwA type gel chromatograph, the number-average molecular weight that records this fluorine-containing aromatic polyester-silicone block copolymer is 145000.
the preparation of oily water separation film and oily water separation experiment:be dissolved in tetrahydrofuran (THF) to be made into massfraction be 1% solution getting above-mentioned product, under magnetic agitation, make fluorine-containing aromatic polyester-silicone block copolymer be dissolved in the inorganic phase of tetrahydrofuran (THF) system.Polymkeric substance is evenly sprayed on 400 object copper mesh with spray gun to dry fluorine-containing aromatic polyester-silicone block copolymer oily water separation film that obtains for 12 hours.(area is 12cm to the oily water separation film of preparation
2) be fixed in homemade oily-water seperating equipment, by dye red water and colourless chloroform (representing polar oil) 1:1 mixing and stirring by volume with red prepared Chinese ink, in 10s, how many 50ml oil-water mixtures are poured in oily-water seperating equipment.Can find that chloroform is also penetrated into and is connect in liquid bottle by separatory membrane rapidly in 10s, and red water is blocked on separatory membrane.
embodiment 3
the preparation of terminal hydroxy group aromatic polyester: first in there-necked flask, add trifluoromethyl Resorcinol 20.32g, 2.60gNaOH, 80 ml deionized waters and 0.06 g phase-transfer catalyst Tetrabutyl amonium bromide, stir and trifluoromethyl Resorcinol is dissolved in water, be made into inorganic phase.4.05g p-phthaloyl chloride and 2.03g letter phthalyl chloride is dissolved in to methylene dichloride 150 ml and is made into certain density organic phase.Be at 10 DEG C, organic phase slowly to be splashed in inorganic phase in temperature, stirring reaction is after 5 hours, after dripping off, 10 DEG C of following reactions 2 hours.Product is washed till to neutrality with dilute hydrochloric acid, obtains terminal hydroxy group aromatic polyester after dry, adopt GPC-MwA type gel chromatograph, recording terminal hydroxy group fluorine-containing aromatic polyester aromatic polyester number-average molecular weight is 17000.
the preparation of fluorine-containing aromatic polyester-silicone block copolymer:hexamethyl vulcabond 0.09g is dissolved in the tetrahydrofuran (THF) of 2g, then in four-hole bottle, add the hexamethyl vulcabond having dissolved, 0.93g hydroxyl-terminated injecting two methyl siloxane (number-average molecular weight is 6000), 95g tetrahydrofuran (THF), dibutyl tin dilaurate 0.03g, stirring is dissolved in hydroxyl-terminated injecting two methyl siloxane in tetrahydrofuran (THF), to be made into inorganic phase and to pass into nitrogen, rising temperature to 80 DEG C is also reacted 2 hours at this temperature, in four-hole bottle, add again the terminal hydroxy group aromatic polyester 5.21g of above-mentioned preparation, temperature remains unchanged, react 3 hours, be cooled to room temperature, employing is revolved and is steamed instrument by the solvents tetrahydrofurane of going out in product, after dry, obtain fluorine-containing aromatic polyester-silicone block copolymer.Adopt GPC-MwA type gel chromatograph, the number-average molecular weight that records this fluorine-containing aromatic polyester-silicone block copolymer is 37000.
oily water separation experiment:by getting above-mentioned product, to be made into massfraction be 20% solution, makes fluorine-containing aromatic polyester-silicone block copolymer be dissolved in the inorganic phase of tetrahydrofuran (THF) system under magnetic agitation.Polymkeric substance is evenly sprayed on 100 object copper mesh with spray gun to dry fluorine-containing aromatic polyester-silicone block copolymer oily water separation film that obtains for 5 hours.(area is 12cm to the oily water separation film of preparation
2) be fixed in homemade oily-water seperating equipment, by dye red water and colourless n-Hexadecane (representing non-polar oil) 1:1 mixing and stirring by volume with red prepared Chinese ink, at 10s, 50ml oil-water mixture is poured in oily-water seperating equipment.Can find that n-Hexadecane is also penetrated into and is connect in liquid bottle by separatory membrane in 10s, and red water is blocked on separatory membrane.
Claims (10)
1. fluorine-containing poly aromatic polyester-silicone block copolymer, is characterized in that, its structural formula as shown in Equation 1;
Formula 1
In formula 1, the random natural number that n is 10-250, the random natural number that m is 50-600;
。
2. fluorine-containing aromatic polyester-silicone block copolymer according to claim 1, is characterized in that, its number-average molecular weight is 20000-180000.
3. fluorine-containing aromatic polyester-silicone block copolymer according to claim 1, is characterized in that, has excellent hydrophobic performance and oleophylic performance.
4. according to the fluorine-containing aromatic polyester-silicone block copolymer described in any one in claim 1-3, it is characterized in that n=100-150, m=300-400.
5. a preparation method for fluorine-containing aromatic polyester-silicone block copolymer described in any one in claim 1-4, after the steps include: hydroxy-terminated polysiloxane, vulcabond, catalysts and solvents to mix, in 60-100 DEG C of reaction 2-5 hour; Then add terminal hydroxy group fluorine-containing aromatic polyester, in 60-100 DEG C of reaction 1-5 hour; And then except desolventizing;
Used catalyst is: dibutyl tin laurate and/or dibutyltin diacetate;
Solvent for use is: one or more in tetrahydrofuran (THF), phenylfluoroform, trichloromethane and methylene dichloride;
The consumption of used catalyst is the 0.1-2% of hydroxy-terminated polysiloxane, vulcabond and the fluorine-containing fragrant total mass of terminal hydroxy group.
6. require the preparation method described in 5 according to power, it is characterized in that, the mol ratio of terminal hydroxy group fluorine-containing aromatic polyester, hydroxy-terminated polysiloxane and vulcabond is 1:0.5-2:2.1-3.
7. require the preparation method described in 5 or 6 according to power, it is characterized in that,
Terminal hydroxy group fluorine-containing aromatic polyester used,
Its structural formula is:
；
In formula,
, the random natural number that n is 10-250;
To be prepared from by copolycondensation by fluorine-containing bis-phenol based compound, m-phthaloyl chloride and p-phthaloyl chloride;
Hydroxy-terminated polysiloxane used is the poly-methyl trifluoro propyl siloxanes of hydroxyl-terminated injecting two methyl siloxane or hydroxyl; Its number-average molecular weight is 3000-40000;
Vulcabond used is the one in tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI) and hexamethyl vulcabond (HDI).
8. require the preparation method described in 7 according to power, it is characterized in that, its specific operation process is as follows:
(1) vulcabond is dissolved in to partial solvent, then adds hydroxy-terminated polysiloxane, catalyzer, stir and form inorganic phase, in 60-100 DEG C of reaction 2-5 hour;
(2) step (1) continues to add remaining solvent and terminal hydroxy group fluorine-containing aromatic polyester after completing, in 60-100 DEG C of reaction 1-5 hour, then except desolventizing obtains fluorine-containing aromatic polyester-silicone block copolymer;
Preferably, the reaction of step (1) is carried out under nitrogen protection condition.
In a claim 1-4 described in any one fluorine-containing aromatic polyester-silicone block copolymer for the application of oily water separation; Concrete, as the application of oily water separation film.
10. an oily water separation film, is characterized in that, is prepared from taking fluorine-containing aromatic polyester-silicone block copolymer described in any one in claim 1-4 as raw material; Concrete is is dissolved in fluorine-containing aromatic polyester-silicone block copolymer described in any one in claim 1-4 that in solvent, to be made into massfraction be 1-25% solution, then this solution is coated in to dry forming in fabric web; Its water contact angle is greater than 120 °, in air to being reduced to below 5 ° in oily contact angle 1s.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680170A (en) * | 2020-12-14 | 2021-04-20 | 山东一诺威新材料有限公司 | Double-component solvent-free hydrophobic boiling-resistant laminating adhesive and preparation method thereof |
| CN116271249A (en) * | 2023-03-28 | 2023-06-23 | 青岛科技大学 | Fluorine oil filled poly (4-hydroxybutyrate) composite fiber membrane patch, preparation method thereof and anti-adhesion membrane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4739013A (en) * | 1985-12-19 | 1988-04-19 | Corvita Corporation | Polyurethanes |
| CN101798375A (en) * | 2010-02-09 | 2010-08-11 | 东莞市贝特利新材料有限公司 | Modified polyurethane |
| CN102115524A (en) * | 2009-12-30 | 2011-07-06 | 上海合达聚合物科技有限公司 | Fluorine-containing polyurethane and preparation method thereof |
| CN102781998A (en) * | 2010-03-09 | 2012-11-14 | 聚合物华润有限公司 | Polyurethane block copolymer based on poly siloxane tenside for membranes |
| CN103524749A (en) * | 2013-10-09 | 2014-01-22 | 济南大学 | Polysiloxane-polyarylester block copolymer, preparation thereof and applications thereof |
-
2014
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4739013A (en) * | 1985-12-19 | 1988-04-19 | Corvita Corporation | Polyurethanes |
| CN102115524A (en) * | 2009-12-30 | 2011-07-06 | 上海合达聚合物科技有限公司 | Fluorine-containing polyurethane and preparation method thereof |
| CN101798375A (en) * | 2010-02-09 | 2010-08-11 | 东莞市贝特利新材料有限公司 | Modified polyurethane |
| CN102781998A (en) * | 2010-03-09 | 2012-11-14 | 聚合物华润有限公司 | Polyurethane block copolymer based on poly siloxane tenside for membranes |
| CN103524749A (en) * | 2013-10-09 | 2014-01-22 | 济南大学 | Polysiloxane-polyarylester block copolymer, preparation thereof and applications thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680170A (en) * | 2020-12-14 | 2021-04-20 | 山东一诺威新材料有限公司 | Double-component solvent-free hydrophobic boiling-resistant laminating adhesive and preparation method thereof |
| CN116271249A (en) * | 2023-03-28 | 2023-06-23 | 青岛科技大学 | Fluorine oil filled poly (4-hydroxybutyrate) composite fiber membrane patch, preparation method thereof and anti-adhesion membrane |
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